TW201706440A - High withstand voltage Schottky barrier diode - Google Patents

High withstand voltage Schottky barrier diode Download PDF

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TW201706440A
TW201706440A TW105107936A TW105107936A TW201706440A TW 201706440 A TW201706440 A TW 201706440A TW 105107936 A TW105107936 A TW 105107936A TW 105107936 A TW105107936 A TW 105107936A TW 201706440 A TW201706440 A TW 201706440A
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layer
gas
single crystal
schottky barrier
withstand voltage
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TWI707057B (en
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佐佐木公平
後藤健
東脇正高
纐纈明伯
熊谷義直
村上尙
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田村製作所股份有限公司
國立研究開發法人情報通信研究機構
國立大學法人東京農工大學
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Abstract

To provide a Ga2O3-based high withstand voltage Schottky barrier diode having excellent withstand voltage characteristics. According to one embodiment of the present invention, provided is a high withstand voltage Schottky barrier diode 1 having: a first layer 10, which is formed of a first Ga2O3-based single crystal containing a first Group IV element, and Cl at a concentration equal to or lower than 5 x 1016 cm-3, and which has an effective donor concentration not lower than 1 x 1013 but not higher than 6.0 x 1017 cm-3; a second layer 12, which is formed of a second Ga2O3-based single crystal containing a second Group IV element, and which has an effective donor concentration that is higher than that of the first layer 10, said second layer being laminated on the first layer 10; an anode electrode 14 formed on the first layer 10; and a cathode electrode 15 formed on the second layer 12.

Description

高耐壓肖特基能障二極體 High withstand voltage Schottky barrier diode

本發明關於高耐壓肖特基能障二極體。 The present invention relates to a high withstand voltage Schottky barrier diode.

先前已知有一種藉由將MBE(Molecular Beam Epitaxy，分子束磊晶)法或EFG(Edge-defined Film-fed Growth，限邊饋膜生長)法作為對Ga2O3系單晶進行摻雜的方法，而在結晶成長的同時添加雜質之方法(例如參照專利文獻1、2)；或是一種在培育Ga2O3系單晶後，藉由離子植入法來添加雜質(摻雜劑)的方法(例如參照專利文獻3)。又，已知有一種由Ga2O3系化合物半導體所構成的肖特基能障二極體(例如參照專利文獻4)。 A method of doping a Ga 2 O 3 single crystal by using an MBE (Molecular Beam Epitaxy) method or an EFG (Edge-defined Film-fed Growth) method is known. Method of adding impurities while crystal growth (for example, refer to Patent Documents 1 and 2); or adding impurities (dopant) by ion implantation after cultivating a Ga 2 O 3 -type single crystal Method (for example, refer to Patent Document 3). Further, a Schottky barrier diode composed of a Ga 2 O 3 based compound semiconductor is known (for example, see Patent Document 4).

[先前技術文獻] [Previous Technical Literature]

(專利文獻) (Patent Literature)

專利文獻1：日本特開2013-56803號公報。 Patent Document 1: Japanese Laid-Open Patent Publication No. 2013-56803.

專利文獻2：日本特開2013-82587號公報。 Patent Document 2: Japanese Laid-Open Patent Publication No. 2013-82587.

專利文獻3：日本特開2013-58637號公報。 Patent Document 3: Japanese Laid-Open Patent Publication No. 2013-58637.

專利文獻4：日本特開2013-102081號公報。 Patent Document 4: Japanese Laid-Open Patent Publication No. 2013-102081.

然而，在MBE法中，容易在磊晶結晶成長中產生雜質偏析(impurity segregation)，因此在深度方向和面內方向(in-plane direction)的雜質濃度分佈的均勻性不佳。 However, in the MBE method, impurity segregation is easily generated in the epitaxial crystal growth, and thus the uniformity of the impurity concentration distribution in the depth direction and the in-plane direction is not good.

又，在EFG法中，由於在原料中含有濃度1×1017cm-3程度的不純物(雜質)，因此無法進行該濃度以下的摻雜。 Further, in the EFG method, since impurities (impurities) having a concentration of about 1 × 10 17 cm -3 are contained in the raw material, doping at a concentration lower than this concentration cannot be performed.

又，在離子植入法中，不純物離子的植入深度被限定在1μm程度。又，由於離子束會對結晶造成傷害，因此會使結晶性劣化。 Further, in the ion implantation method, the implantation depth of the impurity ions is limited to about 1 μm. Further, since the ion beam damages the crystal, the crystallinity is deteriorated.

因此，在先前技術中，無法形成一種Ga2O3系單晶，其含有目標濃度之供體且供體濃度分佈的均勻性高，而難以製造出一種耐電壓特性優異的Ga2O3系的肖特基能障二極體。 Therefore, in the prior art, it is impossible to form a Ga 2 O 3 -based single crystal containing a donor of a target concentration and having a high uniformity of a donor concentration distribution, and it is difficult to produce a Ga 2 O 3 system excellent in withstand voltage characteristics. Schottky barrier diodes.

因此，本發明的其中一個目的在於提供一種耐電壓特性優異的Ga2O3系的高耐壓肖特基能障二極體。 Accordingly, it is an object of the present invention to provide a Ga 2 O 3 -based high withstand voltage Schottky barrier diode excellent in withstand voltage characteristics.

本發明的一態樣，為了達成上述目的而提供下述[1]~[6]之高耐壓肖特基能障二極體。 In one aspect of the present invention, in order to achieve the above object, the high-voltage Schottky barrier diodes of the following [1] to [6] are provided.

[1]一種高耐壓肖特基能障二極體，其具有：第1層，其由第一Ga2O3系單晶所構成，且其實效供體濃度在1×1013cm-3以上且在6.0×1017cm-3以下，其中， 該第一Ga2O3系單晶含有第一IV族元素和濃度5×1016cm-3以下的氯(Cl)；第2層，其由含有第二IV族元素之第二Ga2O3系單晶所構成，且其實效供體濃度高於前述第1層的實效供體濃度，並積層於前述第1層上；陽極電極，其被形成於前述第1層上；及，陰極電極，其被形成於前述第2層上。 [1] A high-withstand voltage Schottky barrier diode having a first layer composed of a first Ga 2 O 3 -based single crystal and having a practical donor concentration of 1 × 10 13 cm - 3 or more and 6.0 × 10 17 cm -3 or less, wherein the first Ga 2 O 3 -based single crystal contains a first group IV element and a concentration of 5 × 10 16 cm -3 or less of chlorine (Cl); the second layer And consisting of a second Ga 2 O 3 single crystal containing a second group IV element, and the effective donor concentration is higher than the effective donor concentration of the first layer, and is laminated on the first layer; An electrode formed on the first layer; and a cathode electrode formed on the second layer.

[2]如前述[1]所述之高耐壓肖特基能障二極體，其中，前述第1層的實效供體濃度在2.0×1016cm-3以下。 [2] The high withstand voltage Schottky barrier diode according to [1] above, wherein the first layer has a effective donor concentration of 2.0 × 10 16 cm -3 or less.

[3]如前述[2]所述之高耐壓肖特基能障二極體，其中，前述第1層的實效供體濃度在1.4×1016cm-3以下。 [3] The high withstand voltage Schottky barrier diode according to the above [2], wherein the effective concentration of the first layer is 1.4 × 10 16 cm -3 or less.

[4]如前述[1]~[3]中任一項所述之高耐壓肖特基能障二極體，其中，前述第一IV族元素為矽(Si)。 [4] The high-voltage Schottky barrier diode according to any one of [1] to [3] wherein the first group IV element is germanium (Si).

[5]如前述[1]~[3]中任一項所述之高耐壓肖特基能障二極體，其中，前述第一Ga2O3系單晶為Ga2O3單晶。 [5] The high-voltage Schottky barrier diode according to any one of [1] to [3] wherein the first Ga 2 O 3 -based single crystal is a Ga 2 O 3 single crystal. .

[6]如前述[1]~[3]中任一項所述之高耐壓肖特基能障二極體，其中，前述陰極電極的與前述第2層接觸之層是由鈦(Ti)所構成。 [6] The high-voltage Schottky barrier diode according to any one of [1] to [3] wherein the layer of the cathode electrode in contact with the second layer is made of titanium (Ti) ) constitutes.

根據本發明，能夠提供一種耐電壓特性優異的Ga2O3系的高耐壓肖特基能障二極體。 According to the present invention, it is possible to provide a Ga 2 O 3 -based high withstand voltage Schottky barrier diode excellent in withstand voltage characteristics.

1‧‧‧高耐壓肖特基能障二極體 1‧‧‧High-voltage Schottky barrier diode

2‧‧‧氣相成長裝置 2‧‧‧Vapor growth device

10‧‧‧第1層(Ga2O3系單晶膜) 10‧‧‧1st layer (Ga 2 O 3 series single crystal film)

11、13‧‧‧面 11, 13 ‧ ‧ face

12‧‧‧第2層(Ga2O3系基板) 12‧‧‧2nd layer (Ga 2 O 3 based substrate)

14‧‧‧陽極 14‧‧‧Anode

15‧‧‧陽極 15‧‧‧Anode

20‧‧‧反應腔室 20‧‧‧Reaction chamber

21‧‧‧第1氣體導入埠 21‧‧‧First gas introduction埠

22‧‧‧第2氣體導入埠 22‧‧‧2nd gas introduction埠

23‧‧‧第3氣體導入埠 23‧‧‧3rd gas introduction埠

24‧‧‧第4氣體導入埠 24‧‧‧4th gas introduction埠

25‧‧‧排氣埠 25‧‧‧Exhaust gas

26‧‧‧反應容器 26‧‧‧Reaction container

27‧‧‧第1加熱手段 27‧‧‧1st heating means

28‧‧‧第2加熱手段 28‧‧‧2nd heating means

R1‧‧‧原料反應區域 R1‧‧‧Material reaction zone

R2‧‧‧結晶成長區域 R2‧‧‧ Crystal Growth Area

第1圖是實施型態之高耐壓肖特基能障二極體1的垂直剖面圖。 Fig. 1 is a vertical sectional view showing a high-voltage Schottky barrier diode 1 of an embodiment.

第2圖是鹵化物氣相磊晶法用之氣相成長裝置的垂直剖面圖。 Fig. 2 is a vertical sectional view of a vapor phase growth apparatus for a vapor phase epitaxy method.

第3圖是表示GaCl的平衡分壓與O2/GaCl供給分壓比之關係之圖表，該分壓比是藉由熱平衡計算而得到，且為Ga2O3結晶成長的環境溫度在1000℃時的結果。 Figure 3 is a graph showing the relationship between the equilibrium partial pressure of GaCl and the partial pressure ratio of O 2 /GaCl supply. The partial pressure ratio is obtained by heat balance calculation, and the ambient temperature for growth of Ga 2 O 3 crystal is 1000 ° C. The result of the time.

第4圖是表示7種肖特基能障二極體的Ga2O3單晶膜的實效供體濃度在深度方向的輪廓之圖表，該輪廓是由電容量-電壓測量結果所算出。 Fig. 4 is a graph showing the profile of the effective donor concentration of the Ga 2 O 3 single crystal film of the seven Schottky barrier diodes in the depth direction, which is calculated from the capacitance-voltage measurement result.

第5圖是表示7種肖特基能障二極體的順向特性之圖表。 Fig. 5 is a graph showing the forward characteristics of seven Schottky barrier diodes.

第6圖是表示7種肖特基能障二極體的逆向特性之圖表。 Fig. 6 is a graph showing the reverse characteristics of seven Schottky barrier diodes.

[實施型態] [implementation type]

(高耐壓肖特基能障二極體的構成) (Structure of high withstand voltage Schottky barrier diode)

第1圖是實施型態之高耐壓肖特基能障二極體1的垂直剖面圖。高耐壓肖特基能障二極體1是縱型的肖特基能障二極體，其具有：第1層10、積層於第1層10上之第2層12、形成於第1層10上之陽極電極14、及形成於第2層12上之陰極電極15。 Fig. 1 is a vertical sectional view showing a high-voltage Schottky barrier diode 1 of an embodiment. The high withstand voltage Schottky barrier diode 1 is a vertical Schottky barrier diode having a first layer 10 and a second layer 12 laminated on the first layer 10 and formed on the first layer The anode electrode 14 on the layer 10 and the cathode electrode 15 formed on the second layer 12.

第1層10是由Ga2O3系單晶所構成，該Ga2O3系單晶含有作為供體之矽(Si)、錫(Sn)等IV族元素。此外，由於已知Sn容易偏析，當使用Sn作為供體時，有第1層10的電特性在面內的均勻性惡化而降低製造良率的風險。因此，更佳是使用Si來作為供體。第1層10的實效供體濃度(Nd-Na)在1×1013cm-3以上且6.0×1017cm-3以下，且較佳為2.0×1016cm-3以下，更佳為1.4×1016cm-3以下。此處，所謂Nd-Na，是供體濃度Nd與受體濃度Na的差值，相當於在實效上發揮功能的供體的濃度。 The first layer 10 is constituted by Ga 2 O 3 single crystal, the single crystal 2 O 3 containing Ga as a donor of silicon (Si), tin (Sn) Group IV elements. Further, since it is known that Sn is easily segregated, when Sn is used as a donor, the electrical characteristics of the first layer 10 are deteriorated in-plane uniformity, and the risk of manufacturing yield is lowered. Therefore, it is more preferable to use Si as a donor. The effective donor concentration (N d -N a ) of the first layer 10 is 1 × 10 13 cm -3 or more and 6.0 × 10 17 cm -3 or less, and preferably 2.0 × 10 16 cm -3 or less, more preferably It is 1.4 × 10 16 cm -3 or less. Here, N d -N a, it is the difference between the donor and the acceptor concentration N d N a concentration, corresponding to exert a function of the concentration of the donor in effectiveness.

當第1層10的Nd-Na在6.0×1017cm-3以下、2.0×1016cm-3以下、1.4×1016cm-3以下、及2.0×1015cm-3以下的情況下，分別能夠將高耐壓能障二極體1的耐壓(耐電壓)作成16V以上、310V以上、360V以上、及440V以上。此處，基於一般性的元件評價基準，將耐電壓定義成：當在高耐壓肖特基能障二極體1的陽極電極14與陰極電極15間流動之逆向漏洩電流的電流密度到達10-3A/cm2時的施加電壓的大小。 When the N d -N a of the first layer 10 is 6.0 × 10 17 cm -3 or less, 2.0 × 10 16 cm -3 or less, 1.4 × 10 16 cm -3 or less, and 2.0 × 10 15 cm -3 or less. In the following, the withstand voltage (withstand voltage) of the high withstand voltage barrier diode 1 can be made 16 V or more, 310 V or more, 360 V or more, and 440 V or more. Here, the withstand voltage is defined as a current density of a reverse leakage current flowing between the anode electrode 14 and the cathode electrode 15 of the high withstand voltage Schottky barrier diode 1 based on a general component evaluation criterion. The magnitude of the applied voltage at -3 A/cm 2 .

此外，為了得到更高的耐電壓特性，亦可設置有電場集中緩和構造，該電場集中緩和構造是將絕緣膜形成於第1層10的表面的陽極電極14的端部上之場板(field plate)構造、及將受體離子植入至第1層10的內部以及第1層10的表面上的陽極電極14的端部上和周邊部之保護環(guard ring)構造等。 Further, in order to obtain higher withstand voltage characteristics, an electric field concentration mitigation structure may be provided, which is a field plate in which an insulating film is formed on the end portion of the anode electrode 14 on the surface of the first layer 10. The plate structure and the guard ring structure in which the acceptor ions are implanted into the inside of the first layer 10 and the end portion of the anode electrode 14 on the surface of the first layer 10 and the peripheral portion.

又，第1層10含有濃度5×1016cm-3以下的氯。這是因為，Ga2O3系單晶膜是藉由HVPE法所形成，且該HVPE法使用含氯之氣體。通常，當藉由HVPE法以外的方法來形成Ga2O3系單晶膜時，不會使用含氯之氣體，因此在Ga2O3系單晶膜中不含氯，或者至少不會含有1×1016cm-3以上的氯。 Further, the first layer 10 contains chlorine having a concentration of 5 × 10 16 cm -3 or less. This is because the Ga 2 O 3 -based single crystal film is formed by the HVPE method, and the HVPE method uses a chlorine-containing gas. In general, when a Ga 2 O 3 -based single crystal film is formed by a method other than the HVPE method, a chlorine-containing gas is not used, so that the Ga 2 O 3 -based single crystal film does not contain chlorine, or at least does not contain 1 × 10 16 cm -3 or more of chlorine.

第1層10的厚度，為了確保讓高耐壓肖特基能障二極體1具有足夠的耐電壓特性，較佳為30nm以上。高耐壓肖特基能障二極體1的耐電壓，是由第1層10的厚度和實效供體濃度(Nd-Na)來決定。例如，當第1層10的Nd-Na為6.0×1017cm-3時，若厚度在30nm以上，則能夠將耐電壓作成21V。此外，第1層10的厚度上限並未特別限定，但由於厚度方向的電阻會隨著厚度增加而增加，因此較佳為在能夠得到被要求的耐電壓特性的範圍中盡可能作得較薄。 The thickness of the first layer 10 is preferably 30 nm or more in order to ensure that the high withstand voltage Schottky barrier diode 1 has sufficient withstand voltage characteristics. The withstand voltage of the high withstand voltage Schottky barrier diode 1 is determined by the thickness of the first layer 10 and the effective donor concentration (N d -N a ). For example, when the N d -N a of the first layer 10 is 6.0 × 10 17 cm -3 , the withstand voltage can be made 21 V when the thickness is 30 nm or more. Further, the upper limit of the thickness of the first layer 10 is not particularly limited, but since the electric resistance in the thickness direction increases as the thickness increases, it is preferable to make it as thin as possible in a range in which the required withstand voltage characteristics can be obtained. .

此處，所謂Ga2O3系單晶，是指Ga2O3單晶或是添加有Al、In等元素而成之Ga2O3單晶。例如，亦可為添加有Al和In而成之Ga2O3單晶也就是(GaxA1yIn(1-x-y))2O3(0<x≦1，0≦y<1，0<x+y≦1)單晶。在添加Al的情況下能隙變寬，而在添加In的情況下能隙變窄。此外，上述Ga2O3單晶，例如具有β型之結晶構造。 Here, the so-called 2 O 3 single crystal Ga, refers to a single crystal or Ga 2 O 3 added with Ga Al, In and the like from the elements 2 O 3 single crystal. For example, it may be a Ga 2 O 3 single crystal in which Al and In are added, that is, (Ga x A1 y In (1-xy) ) 2 O 3 (0<x≦1, 0≦y<1,0 <x+y≦1) single crystal. In the case where Al is added, the energy gap is widened, and in the case where In is added, the energy gap is narrowed. Further, the above Ga 2 O 3 single crystal has, for example, a β-type crystal structure.

第2層12是由第二Ga2O3系單晶所構成，該第二Ga2O3系含有作為供體之Si、Sn等IV族元素。第2 層12的Nd-Na，比第1層10的Nd-Na更高，例如為1×1018cm-3以上且在1.0×1020cm-3以下。第2層12的厚度，例如為50~1000μm。 The second layer 12 is composed of a second Ga 2 O 3 -based single crystal, and the second Ga 2 O 3 contains a group IV element such as Si or Sn as a donor. Layer 2 N d -N a 12, the first layer is higher than 1 N d -N 10 of a, for example, 1 × 10 18 cm -3 or more and 1.0 × 10 20 cm -3 or less. The thickness of the second layer 12 is, for example, 50 to 1000 μm.

由於高耐壓肖特基能障二極體1的耐電壓，幾乎不依存於第1層10和第2層12的主面面晶面方位，因此第1層10和第2層12的主面的晶面方位並未特別限定，例如由結晶成長速度的觀點來看，會作成(001)、(010)、(110)、(210)、(310)、(610)、(910)、(101)、(102)、(201)、(401)、(-101)、(-201)、(-102)或是(-401)。 Since the withstand voltage of the high withstand voltage Schottky barrier diode 1 hardly depends on the principal plane plane orientation of the first layer 10 and the second layer 12, the main layers of the first layer 10 and the second layer 12 The crystal plane orientation of the surface is not particularly limited. For example, from the viewpoint of the crystal growth rate, (001), (010), (110), (210), (310), (610), (910), (101), (102), (201), (401), (-101), (-201), (-102) or (-401).

陽極電極14，被形成於第1層10中的位於與第2層12相反的一側之面也就是面11上，且與第1層10進行肖特基接觸。 The anode electrode 14 is formed on the surface of the first layer 10 on the side opposite to the second layer 12, that is, on the surface 11, and is in Schottky contact with the first layer 10.

陽極電極14，由鉑(Pt)、鎳(Ni)等金屬所構成。陽極電極14，亦可具有積層不同金屬膜而成之多層構造，例如Pt/Au或Pt/Al。 The anode electrode 14 is made of a metal such as platinum (Pt) or nickel (Ni). The anode electrode 14 may have a multilayer structure in which different metal films are laminated, such as Pt/Au or Pt/Al.

陰極電極15，被形成於第2層12中的位於與第1層10相反的一側之面也就是面13上，且與第2層12進行歐姆接觸。 The cathode electrode 15 is formed on the surface of the second layer 12 on the side opposite to the first layer 10, that is, on the surface 13, and is in ohmic contact with the second layer 12.

陰極電極15，由鈦(Ti)等金屬所構成。陰極電極15，亦可具有積層不同金屬膜而成之多層構造，例如Ti/Au或Ti/Al。為了使陰極電極15與第2層12確實地進行歐姆接觸，較佳為陰極電極15的與第2層12接觸之層是由Ti所構成。 The cathode electrode 15 is made of a metal such as titanium (Ti). The cathode electrode 15 may have a multilayer structure in which different metal films are laminated, such as Ti/Au or Ti/Al. In order to make the cathode electrode 15 and the second layer 12 reliably in ohmic contact, it is preferable that the layer of the cathode electrode 15 in contact with the second layer 12 is made of Ti.

在高耐壓肖特基能障二極體1中，藉由在陽極電極14與陰極電極15之間施加順向電壓(陽極電極14側為正電位)，自第1層10觀察到的陽極電極14與第1層10之界面的能量障壁降低，而有電流自陽極電極14流向陰極電極15。另一方面，當在陽極電極14與陰極電極15之間施加逆向電壓(陽極電極14側為負電位)時，因為有肖特基障壁，不會有電流流動。 In the high withstand voltage Schottky barrier diode 1, the anode viewed from the first layer 10 is applied by applying a forward voltage between the anode electrode 14 and the cathode electrode 15 (positive potential on the anode electrode 14 side). The energy barrier at the interface between the electrode 14 and the first layer 10 is lowered, and current flows from the anode electrode 14 to the cathode electrode 15. On the other hand, when a reverse voltage is applied between the anode electrode 14 and the cathode electrode 15 (the anode electrode 14 side has a negative potential), since there is a Schottky barrier, no current flows.

在高耐壓肖特基能障二極體1的典型構成中，第2層12是Ga2O3系基板，第1層10是在第2層12上磊晶成長而成的Ga2O3系單晶膜。此外，在第2層12為Ga2O3系基板的情況下，由於不是藉由HVPE法來形成，因此實質上不含有氯。 In a typical configuration of the high withstand voltage Schottky barrier diode 1, the second layer 12 is a Ga 2 O 3 substrate, and the first layer 10 is Ga 2 O which is epitaxially grown on the second layer 12 . 3 series single crystal film. Further, when the second layer 12 is a Ga 2 O 3 -based substrate, since it is not formed by the HVPE method, chlorine is not substantially contained.

又，作為高耐壓肖特基能障二極體1的其他構成，可能有第1層10與第2層12均為磊晶膜之構成。在此情況下，例如第1層10和第2層12，是藉由在由Ga2O3系單晶所構成的基底基板上進行磊晶成長後，再從該基底基板分離出來而形成。在此情況下，第2層12的厚度，例如為0.1~50μm。 Further, as another configuration of the high withstand voltage Schottky barrier diode 1, the first layer 10 and the second layer 12 may each be an epitaxial film. In this case, for example, the first layer 10 and the second layer 12 are formed by epitaxial growth on a base substrate made of a Ga 2 O 3 single crystal, and then separated from the base substrate. In this case, the thickness of the second layer 12 is, for example, 0.1 to 50 μm.

(高耐壓肖特基能障二極體的製造方法) (Manufacturing method of high withstand voltage Schottky barrier diode)

以下，對高耐壓肖特基能障二極體1的製造方法之一例進行說明。在此例中，是在作為第2層12之Ga2O3系基板上，磊晶成長出作為第1層10之Ga2O3系單晶膜。 Hereinafter, an example of a method of manufacturing the high withstand voltage Schottky barrier diode 1 will be described. In this example, a Ga 2 O 3 -based single crystal film as the first layer 10 is epitaxially grown on the Ga 2 O 3 -based substrate as the second layer 12 .

首先，對藉由FZ(Floating Zone，浮動帶域)法或EFG(Edge Defined Film Fed Growth，限 邊饋膜生長)法等之融液成長法所培育出來的Ga2O3系單晶的塊狀結晶進行切片，並研磨表面，藉此形成作為第2層12之Ga2O3系基板。 First, a block of a Ga 2 O 3 single crystal grown by a melt growth method such as FZ (Floating Zone) or EFG (Edge Defined Film Fed Growth). The crystals were sliced and the surface was polished to form a Ga 2 O 3 -based substrate as the second layer 12.

接著，藉由HVPE(Halide Vapor Phase Epitaxy，鹵化物氣相磊晶)法，在Ga2O3系基板上磊晶成長出作為第1層10之Ga2O3系單晶膜。 Then, a Ga 2 O 3 -based single crystal film as the first layer 10 is epitaxially grown on a Ga 2 O 3 substrate by an HVPE (Halide Vapor Phase Epitaxy) method.

第2圖是HVPE法用之氣相成長裝置2的垂直剖面圖。氣相成長裝置2，具有：反應腔室20，其具有第1氣體導入埠21、第2氣體導入埠22、第3氣體導入埠23、第4氣體導入埠24及排氣埠25；以及，第1加熱手段27和第2加熱手段28，其被設置於反應腔室20的周圍，並對反應腔室20內的規定區域進行加熱。 Fig. 2 is a vertical sectional view of the vapor phase growth apparatus 2 for the HVPE method. The vapor phase growth apparatus 2 includes a reaction chamber 20 having a first gas introduction port 21, a second gas introduction port 22, a third gas introduction port 23, a fourth gas introduction port 24, and an exhaust port 25; The first heating means 27 and the second heating means 28 are provided around the reaction chamber 20 and heat a predetermined area in the reaction chamber 20.

HVPE法，相較於MBE法等，其成膜速率較高。又，膜厚的面內分佈的均勻性較高，而能夠成長出大口徑之膜。因此，適合用於結晶的大量生產。 The HVPE method has a higher film formation rate than the MBE method. Further, the uniformity of the in-plane distribution of the film thickness is high, and a film having a large diameter can be grown. Therefore, it is suitable for mass production of crystallization.

反應腔室20，具有：原料反應區域R1，其配置有收容Ga原料之反應容器26，並產生鎵的原料氣體；及，結晶成長區域R2，其配置有Ga2O3系基板，並進行Ga2O3系單晶膜之成長。反應腔室20，例如由石英玻璃所構成。 The reaction chamber 20 has a raw material reaction region R1 in which a reaction container 26 containing a Ga raw material is disposed, and a raw material gas for generating gallium is disposed, and a crystal growth region R2 in which a Ga 2 O 3 -based substrate is disposed and Ga is formed 2 O 3 series single crystal film growth. The reaction chamber 20 is made of, for example, quartz glass.

此處，反應容器26，例如為石英玻璃，而被收容於反應容器26中之Ga原料為金屬鎵。 Here, the reaction container 26 is, for example, quartz glass, and the Ga raw material accommodated in the reaction container 26 is metal gallium.

第1加熱手段27與第2加熱手段28，能夠分別對反應腔室20的原料反應區域R1與結晶成長區域R2進 行加熱。第1加熱手段27與第2加熱手段28，例如為電阻加熱式或輻射加熱式之加熱裝置。 The first heating means 27 and the second heating means 28 can respectively enter the raw material reaction region R1 and the crystal growth region R2 of the reaction chamber 20 Line heating. The first heating means 27 and the second heating means 28 are, for example, a resistance heating type or a radiant heating type heating means.

第1氣體導入埠21，是用來將Cl2氣體或HCL氣體也就是含氯氣體，利用非活性氣體(惰性氣體)也就是載體氣體(N2氣體、Ar氣體或He氣體)來導入至反應腔室20的原料反應區域R1內之埠。第2氣體導入埠22，是用來將氧氣的原料氣體也就是O2氣體或H2O氣體等之含氧氣體，利用非活性氣體也就是載體氣體(N2氣體、Ar氣體或He氣體)來導入至反應腔室20的結晶成長區域R2內之埠。第3氣體導入埠23，是用來將非活性氣體也就是載體氣體(N2氣體、Ar氣體或He氣體)導入至反應腔室20的結晶成長區域R2內之埠。第4氣體導入埠24，是用來將對於Ga2O3系單晶膜而言是雜質的矽(Si)等的原料氣體(例如四氯化矽等)，利用非活性氣體也就是載體氣體(N2氣體、Ar氣體或He氣體)來導入至反應腔室20的結晶成長區域R2內之埠。 The first gas introduction port 21 is for introducing a Cl 2 gas or a HCL gas, that is, a chlorine-containing gas, into an reaction using an inert gas (inert gas), that is, a carrier gas (N 2 gas, Ar gas or He gas). The raw material in the chamber 20 is in the reaction zone R1. The second gas introduction port 22 is an oxygen-containing gas for oxygen source gas, that is, O 2 gas or H 2 O gas, and is an inert gas, that is, a carrier gas (N 2 gas, Ar gas or He gas). It is introduced into the crystal growth region R2 of the reaction chamber 20. The third gas introduction port 23 is for introducing an inert gas, that is, a carrier gas (N 2 gas, Ar gas or He gas) into the crystal growth region R2 of the reaction chamber 20 . The fourth gas introduction port 24 is a material gas (for example, antimony tetrachloride or the like) such as antimony (Si) which is an impurity to the Ga 2 O 3 -based single crystal film, and an inert gas, that is, a carrier gas. (N 2 gas, Ar gas, or He gas) is introduced into the crystal growth region R2 of the reaction chamber 20 .

針對Ga2O3系單晶膜的成長，能夠使用日本特願2014-088589所揭示之Ga2O3系單晶膜的成長技術。以下，對本實施型態之Ga2O3系單晶膜的成長步驟的一例進行說明。 Growth for Ga 2 O 3 single crystal film can be used as disclosed in Japanese Patent Application No. 2014-088589 of Ga 2 O 3 system single crystal film growth techniques. Hereinafter, an example of the growth step of the Ga 2 O 3 -based single crystal film of the present embodiment will be described.

首先，使用第1加熱手段27對反應腔室20的原料反應區域R1進行加熱，並將原料反應區域R1的環境溫度保持於規定溫度。 First, the raw material reaction region R1 of the reaction chamber 20 is heated by the first heating means 27, and the ambient temperature of the raw material reaction region R1 is maintained at a predetermined temperature.

接著，利用載體氣體自第1氣體導入埠21導入含氯氣體，於原料反應區域R1中，在上述環境溫度下使反應容器26內之金屬鎵與含氯氣體進行反應，而產生氯化鎵系氣體。 Next, a chlorine-containing gas is introduced from the first gas introduction port 21 by the carrier gas, and the metal gallium in the reaction container 26 is reacted with the chlorine-containing gas at the ambient temperature in the raw material reaction region R1 to produce a gallium chloride system. gas.

此時，上述原料反應區域R1內的環境溫度，較佳為能夠使得在由反應容器26內之金屬鎵與含氯氣體的反應所產生之氯化鎵系氣體中，是GaCl氣體的分壓變成最高的溫度。此處，在氯化鎵系氣體中，含有GaCl氣體、GaCl2氣體、GaCl3氣體、(GaCl3)2氣體等。 In this case, the ambient temperature in the raw material reaction region R1 is preferably such that the partial pressure of the GaCl gas in the gallium chloride-based gas generated by the reaction between the metal gallium and the chlorine-containing gas in the reaction vessel 26 becomes The highest temperature. Here, the gallium chloride-based gas contains GaCl gas, GaCl 2 gas, GaCl 3 gas, (GaCl 3 ) 2 gas, or the like.

GaCl氣體，是在氯化鎵系氣體所含之氣體中，能夠將Ga2O3結晶的成長驅動力保持到最高溫度之氣體。為了得到高純度、高品質的Ga2O3結晶，在較高成長溫度下的成長是有效的，因此產生在高溫中成長驅動力較高的GaCl氣體的分壓較高之氯化鎵系氣體，對於Ga2O3系單晶膜的成長是較佳的。 The GaCl gas is a gas capable of maintaining the growth driving force of the Ga 2 O 3 crystal to the highest temperature among the gases contained in the gallium chloride-based gas. In order to obtain high-purity, high-quality Ga 2 O 3 crystals, growth at a higher growth temperature is effective, so that a gallium chloride-based gas having a higher partial pressure of GaCl gas having a higher growth driving force at a high temperature is generated. It is preferable for the growth of the Ga 2 O 3 -based single crystal film.

藉由在約300℃以上的環境溫度下使金屬鎵與含氯氣體進行反應，能夠提高氯化鎵系氣體中的GaCl氣體的分壓比。因此，較佳為在藉由第1加熱手段27將原料反應區域R1的環境溫度保持在300℃以上的狀態下，使反應容器26內之金屬鎵與含氯氣體進行反應。 By reacting metal gallium with a chlorine-containing gas at an ambient temperature of about 300 ° C or higher, the partial pressure ratio of GaCl gas in the gallium chloride-based gas can be increased. Therefore, it is preferable to react the metal gallium in the reaction container 26 with the chlorine-containing gas while maintaining the ambient temperature of the raw material reaction region R1 at 300 ° C or higher by the first heating means 27 .

此外，例如，在850℃的環境溫度下，GaCl氣體的分壓比會壓倒性地變高(GaCl氣體的平衡分壓比GaCl2氣體大了4個數量級，且比GaCl3氣體大了8個數 量級)，因此GaCl氣體以外之氣體幾乎不會對Ga2O3結晶的成長作出貢獻。 In addition, for example, at an ambient temperature of 850 ° C, the partial pressure ratio of GaCl gas is overwhelmingly higher (the equilibrium partial pressure of GaCl gas is 4 orders of magnitude larger than that of GaCl 2 gas, and 8 times larger than GaCl 3 gas. It is of the order of magnitude), and therefore gases other than GaCl gas hardly contribute to the growth of Ga 2 O 3 crystals.

又，考慮到第1加熱手段27的壽命或是由石英玻璃等所構成之反應腔室20的耐熱性，較佳為在將原料反應區域R1的環境溫度保持在1000℃以下的狀態下，使反應容器26內之金屬鎵與含氯氣體進行反應。 Further, in consideration of the life of the first heating means 27 or the heat resistance of the reaction chamber 20 made of quartz glass or the like, it is preferable to maintain the ambient temperature of the raw material reaction region R1 at 1000 ° C or lower. The metal gallium in the reaction vessel 26 reacts with a chlorine-containing gas.

又，若在使Ga2O3系單晶膜成長時的環境中含有氫氣，則Ga2O3系單晶膜的表面平坦性和結晶成長驅動力會降低，因此較佳為使用不含氫之Cl2氣體來作為含氯氣體。 In addition, when hydrogen gas is contained in the environment when the Ga 2 O 3 -based single crystal film is grown, the surface flatness and the crystal growth driving force of the Ga 2 O 3 -based single crystal film are lowered. Therefore, it is preferable to use hydrogen-free. The Cl 2 gas is used as a chlorine-containing gas.

接著，在結晶成長區域R2中，使在原料反應區域R1中所產生之氯化鎵系氣體、自第2氣體導入埠22所導入之含氧氣體、及自第4氣體導入埠24所導入之Si等之雜質的原料氣體混合，並將Ga2O3系基板曝露於該混合氣體中，而在Ga2O3系基板上磊晶成長出含雜質之Ga2O3系單晶膜。此時，收容反應腔室20之爐內的結晶成長區域R2中的壓力，例如保持在1atm。 Next, in the crystal growth region R2, the gallium chloride-based gas generated in the raw material reaction region R1, the oxygen-containing gas introduced from the second gas introduction port 22, and the fourth gas introduced into the crucible 24 are introduced. A raw material gas of an impurity such as Si is mixed, and a Ga 2 O 3 -based substrate is exposed to the mixed gas, and a Ga 2 O 3 -based single crystal film containing impurities is epitaxially grown on the Ga 2 O 3 -based substrate. At this time, the pressure in the crystal growth region R2 in the furnace in which the reaction chamber 20 is housed is maintained at, for example, 1 atm.

此處，作為雜質的原料氣體，為了抑制非預期的其他不純物混入，較佳為使用氯化物系氣體，例如將Si、Ge、Sn或Pb作為雜質的情況下，分別使用SiCl4、GeCl4、SnCl4、PbCl2等之氯化物系氣體。又，氯化物系氣體，並不限於僅與氯化合者，例如亦可使用SiHCl3等之矽烷系氣體。 Here, as the source gas of the impurity, in order to suppress the inadvertent addition of other impurities, it is preferable to use a chloride-based gas. For example, when Si, Ge, Sn, or Pb is used as an impurity, SiCl 4 or GeCl 4 is used, respectively. a chloride-based gas such as SnCl 4 or PbCl 2 . Further, the chloride-based gas is not limited to being chlorinated only, and for example, a decane-based gas such as SiHCl 3 may be used.

Si等之雜質，是與Ga2O3系單晶之成長並行地進行摻雜(in situ doping，原位摻雜) The impurity of Si or the like is doped in parallel with the growth of the Ga 2 O 3 single crystal (in situ doping)

此外，若在使Ga2O3系單晶膜成長時的環境中含有氫氣，則Ga2O3系單晶膜的表面平坦性和結晶成長驅動力會降低，因此較佳為使用不含氫之O2氣體來作為含氧氣體。 In addition, when hydrogen gas is contained in the environment when the Ga 2 O 3 -based single crystal film is grown, the surface flatness and the crystal growth driving force of the Ga 2 O 3 -based single crystal film are lowered, so that it is preferable to use hydrogen-free. The O 2 gas is used as an oxygen-containing gas.

又，GaCl氣體的平衡分壓越小，則GaCl氣體越會被消費於Ga2O3結晶的成長中，而使Ga2O3有效率地進行成長。例如，若O2氣體的供給分壓相對於GaCl氣體的供給分壓之比值(O2/GaCl供給分壓比)成為0.5以上，則GaCl氣體的平衡分壓會急劇降低。因此，為了有效率地使Ga2O3系單晶膜進行成長，較佳為在結晶成長區域R2中的O2/GaCl供給分壓比在0.5以上的狀態下使Ga2O3系單晶膜進行成長。 Further, the smaller the equilibrium partial pressure of the GaCl gas, the more the GaCl gas is consumed in the growth of the Ga 2 O 3 crystal, and the Ga 2 O 3 is efficiently grown. For example, when the ratio of the supply partial pressure of the O 2 gas to the supply partial pressure of the GaCl gas (O 2 /GaCl supply partial pressure ratio) is 0.5 or more, the equilibrium partial pressure of the GaCl gas is drastically lowered. Therefore, in order to efficiently grow the Ga 2 O 3 -based single crystal film, it is preferable to make the Ga 2 O 3 single crystal in a state where the O 2 /GaCl supply partial pressure ratio in the crystal growth region R2 is 0.5 or more. The film grows.

第3圖是表示GaCl的平衡分壓與O2/GaCl供給分壓比之關係之圖表，該分壓比是藉由熱平衡計算所得到，且為Ga2O3結晶成長的環境溫度在1000℃時之結果。在本計算中，將GaCl氣體的供給分壓值固定在1×10-3atm，並利用例如N2等之非活性氣體來作為載體氣體且將爐內壓力設為1atm，並改變O2氣體的供給分壓值。 Figure 3 is a graph showing the relationship between the equilibrium partial pressure of GaCl and the partial pressure ratio of O 2 /GaCl supply. The partial pressure ratio is obtained by heat balance calculation, and the ambient temperature for growth of Ga 2 O 3 crystal is 1000 ° C. The result of the time. In the present calculation, the supply partial pressure value of GaCl gas is fixed at 1 × 10 -3 atm, and an inert gas such as N 2 is used as a carrier gas and the pressure in the furnace is set to 1 atm, and the O 2 gas is changed. The supply partial pressure value.

第3圖的橫軸表示O2/GaCl供給分壓比，縱軸表示GaCl氣體的平衡分壓(atm)。GaCl氣體的平衡 分壓越小，表示GaCl氣體越會被消費於Ga2O3結晶的成長中，亦即，Ga2O3結晶有效率地成長。 The horizontal axis of Fig. 3 represents the O 2 /GaCl supply partial pressure ratio, and the vertical axis represents the equilibrium partial pressure (atm) of the GaCl gas. The smaller the equilibrium partial pressure of GaCl gas, it represents GaCl gas consumption will be more growth of Ga 2 O 3 in the crystalline, i.e., Ga 2 O 3 crystals to grow efficiently.

第3圖表示若O2/GaCl供給分壓比變成0.5以上，則GaCl氣體的平衡分壓便會急劇降低。 Fig. 3 shows that if the O 2 /GaCl supply partial pressure ratio becomes 0.5 or more, the equilibrium partial pressure of the GaCl gas is drastically lowered.

又，為了使Ga2O3系單晶膜成長，要求成長溫度在900℃以上。在低於900℃的情況下，有無法得到單晶的風險。 Further, in order to grow the Ga 2 O 3 -based single crystal film, the growth temperature is required to be 900 ° C or higher. At less than 900 ° C, there is a risk that a single crystal cannot be obtained.

此外，以HVPE法成長出來的非摻雜的Ga2O3系單晶膜，如日本特願2014-088589所揭示，其殘留載體濃度在1×1013cm-3以下。因此，藉由改變IV族元素的摻雜濃度，Ga2O3系單晶膜的Nd-Na能夠在1×1013cm-3以上的範圍中進行變化。 Further, the undoped Ga 2 O 3 -based single crystal film grown by the HVPE method has a residual carrier concentration of 1 × 10 13 cm -3 or less as disclosed in Japanese Patent Application No. 2014-088589. Therefore, by changing the doping concentration of the group IV element, the N d -N a of the Ga 2 O 3 -based single crystal film can be changed in the range of 1 × 10 13 cm -3 or more.

在Ga2O3系基板上成長出Ga2O3系單晶膜後，藉由CMP(Chemical Mechanical Polishing，化學機械研磨)使Ga2O3系單晶膜的表面平坦化。例如，藉由在深度方向研磨2μm程度，表面粗糙度(RMS)會成為1nm以下。利用平坦化處理來縮小表面粗糙度，當對陽極電極施加逆向電壓時，便能藉此使電場不容易集中於局部，而提高肖特基能障二極體的耐電壓。此外，在剛成長完成時的RMS便為1nm以下的情況下，亦可不進行平坦化處理。 After growth of the Ga 2 O 3 single crystal film on the Ga 2 O 3 based substrate, by CMP (Chemical Mechanical Polishing, chemical mechanical polishing) Ga 2 O 3 system single crystal film is planarized surface. For example, by grinding in the depth direction by about 2 μm, the surface roughness (RMS) becomes 1 nm or less. By flattening the surface roughness, when a reverse voltage is applied to the anode electrode, the electric field is not easily concentrated locally, and the withstand voltage of the Schottky barrier diode is increased. Further, in the case where the RMS at the time of completion of growth is 1 nm or less, the planarization treatment may not be performed.

又，較佳為針對Ga2O3系基板中的位於與Ga2O3系單晶膜相反的一側之面，亦施行研磨處理。有時會因為Ga2O3系單晶膜的HVPE成長中之原料氣體繞 到裏側(背面側)，而在基板背面產生預期之外的附著物，所以在未進行研磨處理的情況下，有與陽極電極的接觸電阻增加的風險。在進行過研磨處理的情況下，便能夠除去該等附著物，而能夠穩定地形成接觸電阻低的陽極電極。此外，朝向深度方向的研磨量沒有特別限定，至少研磨1μm以上便能夠達成本目的。 Further, it is preferable to perform a polishing treatment on the surface of the Ga 2 O 3 -based substrate on the side opposite to the Ga 2 O 3 -based single crystal film. In some cases, the raw material gas in the HVPE growth of the Ga 2 O 3 single crystal film is wound around the back side (back side), and an unexpected deposit is generated on the back surface of the substrate. Therefore, in the case where the polishing treatment is not performed, there is The risk of increased contact resistance with the anode electrode. When the polishing treatment is performed, the deposits can be removed, and the anode electrode having a low contact resistance can be stably formed. Further, the amount of polishing in the depth direction is not particularly limited, and the object can be attained by polishing at least 1 μm.

接著，在作為第1層10之Ga2O3系單晶膜的面11上及作為第2層12之Ga2O3系基板的面13上，分別形成陽極電極14與陰極電極15。 Next, the anode electrode 14 and the cathode electrode 15 are formed on the surface 11 of the Ga 2 O 3 -based single crystal film as the first layer 10 and on the surface 13 of the Ga 2 O 3 -based substrate as the second layer 12, respectively.

此外，在第2層12為磊晶層的情況下，與上述第1層10的形成方法同樣地藉由HVPE法來形成於基底基板上。此基底基板，在形成陰極電極15前，自第2層12分離。 Further, when the second layer 12 is an epitaxial layer, it is formed on the base substrate by the HVPE method in the same manner as the method of forming the first layer 10 described above. This base substrate is separated from the second layer 12 before the cathode electrode 15 is formed.

(實施型態的功效) (Effect of implementation type)

根據上述實施型態，藉由使用HVPE法來一邊成長Ga2O3系單晶一邊添加雜質，便能夠得到含有目的濃度之供體，且供體濃度分佈的均勻性高之第1層10，或是得到具有上述特徵之第1層10和第2層12。藉此，能夠得到耐電壓特性優異的高耐壓肖特基能障二極體1。 According to the above-described embodiment, by adding an impurity while growing a Ga 2 O 3 single crystal by using the HVPE method, it is possible to obtain a first layer 10 having a donor having a target concentration and having a high uniformity of a donor concentration distribution. Or the first layer 10 and the second layer 12 having the above characteristics are obtained. Thereby, the high withstand voltage Schottky barrier diode 1 excellent in withstand voltage characteristics can be obtained.

[實施例] [Examples]

以下，作為實施例來描述上述實施型態之高耐壓肖特基能障二極體1的一型態的製造和評價結果。本實施例中，是在作為第2層12之主面的晶面方位為(001)之 Ga2O3基板上，磊晶成長出作為第1層10之Ga2O3單晶膜。 Hereinafter, the manufacturing and evaluation results of one type of the high-voltage Schottky barrier diode 1 of the above-described embodiment will be described as an embodiment. In the present embodiment, a Ga 2 O 3 single crystal film as the first layer 10 is epitaxially grown on a Ga 2 O 3 substrate having a crystal plane orientation of (001) as the main surface of the second layer 12.

首先，使用EFG法培育出摻雜有Sn之Ga2O3單晶，並施行切片與研磨加工，而製作出複數片Ga2O3基板。Ga2O3基板的Nd-Na，作成約2.5×1018cm-3。Ga2O3基板的厚度，作成約650μm。 First, a Ga 2 O 3 single crystal doped with Sn was grown by an EFG method, and slicing and polishing were performed to fabricate a plurality of Ga 2 O 3 substrates. The N d -N a of the Ga 2 O 3 substrate was made to be about 2.5 × 10 18 cm -3 . The thickness of the Ga 2 O 3 substrate was set to be about 650 μm.

接著，使用HVPE法，在複數片Ga2O3基板上成長出厚度10μm程度的摻雜有Si之Ga2O3單晶膜。Ga2O3單晶膜的Si濃度，作成約2.0×1015cm-3、1.4×1016cm-3、2.0×1016cm-3、1.0×1017cm-3、1.5×1017cm-3、2.9×1017cm-3或是6.0×1017cm-3。 Next, a Si-doped Ga 2 O 3 single crystal film having a thickness of about 10 μm was grown on a plurality of Ga 2 O 3 substrates by the HVPE method. The Si concentration of the Ga 2 O 3 single crystal film is about 2.0 × 10 15 cm -3 , 1.4 × 10 16 cm -3 , 2.0 × 10 16 cm -3 , 1.0 × 10 17 cm -3 , 1.5 × 10 17 cm . -3 , 2.9 × 10 17 cm -3 or 6.0 × 10 17 cm -3 .

HVPE成長後，針對自Ga2O3單晶膜的表面起到深度2~3μm程度的部分，施行CMP處理，使其平坦化。又，對於Ga2O3基板中的位於Ga2O3單晶膜的相反一側之面，亦針對自表面起到深度50μm程度的部分，施行研削、研磨、CMP處理，使其平坦化。 After the HVPE is grown, a portion having a depth of about 2 to 3 μm from the surface of the Ga 2 O 3 single crystal film is subjected to CMP treatment to planarize it. Further, the surface on the opposite side of the Ga 2 O 3 single crystal film in the Ga 2 O 3 substrate was also subjected to grinding, polishing, and CMP treatment to planarize the portion having a depth of about 50 μm from the surface.

接著，在Ga2O3基板上，藉由蒸鍍來形成陽極電極，該陽極電極積層了厚度20nm的Ti膜與厚度230nm的Au膜。 Next, an anode electrode was formed on the Ga 2 O 3 substrate by vapor deposition, and the anode electrode was laminated with a Ti film having a thickness of 20 nm and an Au film having a thickness of 230 nm.

接著，在Ga2O3基板上，形成圓形的陽極電極，該陽極電極積層了厚度15nm的Pt膜、厚度5nm的Ti膜及厚度250nm的Au膜。關於陽極電極的直徑，將電流-電壓(I-V)測量用的電極作成200μm，並將電容量-電壓(C-V)測量用的電極作成400μm。 Next, on the Ga 2 O 3 substrate, a circular anode electrode was formed, which was laminated with a Pt film having a thickness of 15 nm, a Ti film having a thickness of 5 nm, and an Au film having a thickness of 250 nm. Regarding the diameter of the anode electrode, an electrode for measuring current-voltage (IV) was made to be 200 μm, and an electrode for measuring capacitance-voltage (CV) was made to be 400 μm.

藉由上述步驟，得到具有不同Si濃度之7種肖特基能障二極體。 Through the above steps, seven Schottky barrier diodes having different Si concentrations are obtained.

第4圖是表示7種肖特基能障二極體之Ga2O3單晶膜的Nd-Na在深度方向的輪廓之圖表，上述輪廓是由C-V測量結果所算出。7種肖特基能障二極體的Ga2O3單晶膜的Nd-Na，分別為約2.0×1015cm-3、1.4×1016cm-3、2.0×1016cm-3、1.0×1017cm-3、1.5×1017cm-3、2.9×1017cm-3、6.0×1017cm-3。 Fig. 4 is a graph showing the outline of the N d -N a of the Ga 2 O 3 single crystal film of the seven types of Schottky barrier diodes in the depth direction, which is calculated from the CV measurement results. The N d -N a of the Ga 2 O 3 single crystal films of the seven Schottky barrier diodes are about 2.0×10 15 cm -3 , 1.4×10 16 cm -3 , and 2.0×10 16 cm - respectively. 3 , 1.0 × 10 17 cm -3 , 1.5 × 10 17 cm -3 , 2.9 × 10 17 cm -3 , 6.0 × 10 17 cm -3 .

第5圖是表示7種肖特基能障二極體的順向特性之圖表。第5圖中的虛線的斜率，表示肖特基能障二極體的理想因子(ideality factor)n為1(理想值)時，電壓低於起始電壓(turn-on voltage)之一側的I-V特性的斜率。根據第5圖，Nd-Na在2.0×1016cm-3以下之肖特基能障二極體中，肖特基的理想因子為1.01~1.03的程度，形成理想的肖特基接觸。另一方面，Nd-Na在1×1017cm-3以上之肖特基能障二極體中，因為漏洩電流的影響，理想因子為1.2的程度。 Fig. 5 is a graph showing the forward characteristics of seven Schottky barrier diodes. The slope of the broken line in Fig. 5 indicates that the ideality factor n of the Schottky barrier diode is 1 (ideal value), and the voltage is lower than one side of the turn-on voltage. The slope of the IV characteristic. The section of FIG. 5, N d -N a Schottky barrier diode can be 2.0 × 10 16 cm -3 or less in the ideality factor is the degree of Schottky 1.01 to 1.03, preferably form a Schottky contact . On the other hand, N d -N a to 1 × 10 17 cm -3 or more of the Schottky barrier diode, since the influence of the leakage current, ideality factor of 1.2 degree.

第6圖是表示7種肖特基能障二極體的逆向特性之圖表。伴隨供體濃度降低，逆向漏洩電流減少，且耐電壓增加。耐電壓，是各輪廓中在電流密度為10-3A/cm2時的電壓大小。 Fig. 6 is a graph showing the reverse characteristics of seven Schottky barrier diodes. As the donor concentration decreases, the reverse leakage current decreases and the withstand voltage increases. The withstand voltage is the voltage at each current density of 10 -3 A/cm 2 in each profile.

根據第6圖，Nd-Na為2.0×1015cm-3之肖特基能障二極體中的耐電壓約為440V，Nd-Na為1.4×1016cm-3之肖特基能障二極體中的耐電壓約為360V， Nd-Na為2.0×1016cm-3之肖特基能障二極體中的耐電壓約為310V，Nd-Na為1.0×1017cm-3之肖特基能障二極體中的耐電壓約為74V，Nd-Na為1.5×1017cm-3之肖特基能障二極體中的耐電壓約為46V，Nd-Na為2.9×1017cm-3之肖特基能障二極體中的耐電壓約為36V，Nd-Na為6.0×1017cm-3之肖特基能障二極體中的耐電壓約為16V。 The first to FIG 6, N d -N a of 2.0 × 10 15 cm -3 withstand voltage of the Schottky barrier diode is about 440V, N d -N a Shore 1.4 × 10 16 cm -3 of The withstand voltage in the special dysfunction diode is about 360V, and the withstand voltage in the Schottky barrier diode with N d -N a of 2.0 × 10 16 cm -3 is about 310V, N d -N a Resistance in a Schottky barrier diode of 1.0 × 10 17 cm -3 in a Schottky barrier diode with a withstand voltage of approximately 74 V and a N d -N a of 1.5 × 10 17 cm -3 voltage of about 46V, N d -N a of 2.9 × 10 17 cm withstand voltage in the energy barrier diode of Schottky-3 is about 36V, N d -N a of 6.0 × 10 17 cm -3 of Shaw The withstand voltage in the special barrier diode is about 16V.

此外，上述評價中，是使用主面的晶面方位為(001)之Ga2O3基板來作為Ga2O3系基板，但即便是在使用其他Ga2O3系基板來取代Ga2O3基板之情況下，以及主面的晶面方位不同的情況下，仍然會得到同樣的評價結果。又，即便在形成其他Ga2O3系單晶膜來取代Ga2O3單晶膜的情況下，仍然會得到同樣的評價結果。 Further, in the above evaluation, a Ga 2 O 3 substrate having a crystal plane orientation of (001) on the principal surface was used as the Ga 2 O 3 substrate, but the Ga 2 O 3 substrate was used instead of Ga 2 O. In the case of the 3 substrates, and the crystal plane orientation of the main surface is different, the same evaluation result is obtained. Further, even when another Ga 2 O 3 -based single crystal film was formed instead of the Ga 2 O 3 single crystal film, the same evaluation results were obtained.

又，上述評價中，是將Ga2O3單晶膜的Nd-Na作成2.0×1015~6.0×1017cm-3，但若使用Nd-Na更低的Ga2O3單晶膜，便能夠得到更高的耐電壓。 Further, in the above evaluation, the N d -N a of the Ga 2 O 3 single crystal film was made 2.0 × 10 15 to 6.0 × 10 17 cm -3 , but if Ga 2 O 3 having a lower N d -N a was used, A single crystal film can obtain a higher withstand voltage.

以上，說明了本發明的實施型態，但本發明並不限定於上述實施型態，在不脫離發明主旨的範圍內可以有各種變化的實施方式。 The embodiments of the present invention have been described above, but the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit and scope of the invention.

又，上述記載的實施型態並不是用來限定申請專利範圍的發明。又，應注意的是，用於解決發明的問題的手段中，並不一定需要實施型態中所說明過的特徵的全部組合。 Further, the above-described embodiments are not intended to limit the scope of the invention. Further, it should be noted that all means for solving the problems of the invention do not necessarily require all combinations of the features described in the embodiments.

1‧‧‧高耐壓肖特基能障二極體 1‧‧‧High-voltage Schottky barrier diode

10‧‧‧第1層(Ga2O3系單晶膜) 10‧‧‧1st layer (Ga 2 O 3 series single crystal film)

11、13‧‧‧面 11, 13 ‧ ‧ face

12‧‧‧第2層(Ga2O3系基板) 12‧‧‧2nd layer (Ga 2 O 3 based substrate)

14‧‧‧陽極電極 14‧‧‧Anode electrode

15‧‧‧陰極電極 15‧‧‧Cathode electrode

Claims (6)

一種高耐壓肖特基能障二極體，其具有：第1層，其由第一Ga2O3系單晶所構成，且其實效供體濃度在1×1013cm-3以上且在6.0×1017cm-3以下，其中，該第一Ga2O3系單晶含有第一IV族元素和濃度5×1016cm-3以下的氯；第2層，其由含有第二IV族元素之第二Ga2O3系單晶所構成，且其實效供體濃度高於前述第1層的實效供體濃度，並積層於前述第1層上；陽極電極，其被形成於前述第1層上；及，陰極電極，其被形成於前述第2層上。 A high-voltage Schottky barrier diode having a first layer composed of a first Ga 2 O 3 -based single crystal and having a practical donor concentration of 1×10 13 cm −3 or more and And 6.0 × 10 17 cm -3 or less, wherein the first Ga 2 O 3 -based single crystal contains a first group IV element and a concentration of 5 × 10 16 cm -3 or less of chlorine; and the second layer contains a second layer a second Ga 2 O 3 single crystal of a group IV element, wherein the effective donor concentration is higher than the effective donor concentration of the first layer, and is laminated on the first layer; the anode electrode is formed on the anode electrode And the cathode electrode is formed on the second layer. 如請求項1所述之高耐壓肖特基能障二極體，其中，前述第1層的實效供體濃度在2.0×1016cm-3以下。 The high withstand voltage Schottky barrier diode according to claim 1, wherein the effective concentration of the first layer is 2.0 × 10 16 cm -3 or less. 如請求項2所述之高耐壓肖特基能障二極體，其中，前述第1層的實效供體濃度在1.4×1016cm-3以下。 The high withstand voltage Schottky barrier diode according to claim 2, wherein the effective concentration of the first layer is 1.4 × 10 16 cm -3 or less. 如請求項1~3中任一項所述之高耐壓肖特基能障二極體，其中，前述第一IV族元素為矽。 The high-voltage Schottky barrier diode according to any one of claims 1 to 3, wherein the first group IV element is germanium. 如請求項1~3中任一項所述之高耐壓肖特基能障二極體，其中，前述第一Ga2O3系單晶為Ga2O3單晶。 The high-voltage Schottky barrier diode according to any one of claims 1 to 3, wherein the first Ga 2 O 3 -based single crystal is a Ga 2 O 3 single crystal. 如請求項1~3中任一項所述之高耐壓肖特基能障二極體，其中，前述陰極電極的與前述第2層接觸之層是由鈦所構成。 The high withstand voltage Schottky barrier diode according to any one of claims 1 to 3, wherein the layer of the cathode electrode in contact with the second layer is made of titanium.
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